Pre-fiber gel materials and compositions, methods of manufacture and uses thereof

ABSTRACT

A pre-fiber gel material is described herein that includes: a) at least one amide-based and/or polyamide-based composition; and b) at least one lactam gelling agent, wherein the gel composition has sufficient viscosity and sufficient cohesiveness upon the mixing of the at least one amide-based or polyamide-based polymer and the at least one lactam gelling agent that the composition can be spun into a fiber. In addition, methods are provided herein that teach that the production of a pre-fiber gel composition, including: a) providing at least one amide-based compound; b) providing at least one lactam gelling agent; and c) mixing the at least one amide-based polymer and the at least one lactam gelling agent such that there is sufficient viscosity and sufficient cohesiveness in the composition so that it can be spun into a fiber.

FIELD OF THE SUBJECT MATTER

The field of the subject matter herein is pre-fiber gel materials andcompositions, fiber products, yarn products and carpet products, methodsof manufacture and uses thereof.

BACKGROUND

Fibers for consumer use and the constituents that make up those fibers,especially fibers and polymers that are incorporated into carpetproducts and fabrics/textiles, are constantly being evaluated forimprovements with respect to the durability and strength. Theseimprovements may relate to tensile strength and tensile properties,quality, durability. Fibers and fiber products are also being evaluatedto determine if there are more efficient and cost-effectivemanufacturing processes and equipment.

Most polymer processing does not only shape polymer into the desiredshape (eg: injection molding, film blowing, fiber spinning, etc.). Theprocessing is usually designed to impart desirable properties to thefinished article by manipulation of the polymer molecules during theforming operation. For example, film blowing is carefully designed tocombine the proper degree of stretching during the cooling of the moltenpolymer. This stretching orients the polymers improving strength andtoughness of the film. Fiber is drawn during the cooling stage tocontrol the degree of crystallization in the finished yarn.

Simple melt processing of polymers has distinct limitations. Since themanipulation is carried out during the brief period of solidification,practical limitations exist on how much molecular orientation can beachieved and/or how much shape manipulation can realized before thepolymer is too cool to accomplish either. To be processed, the polymermust melt, the molecules freed-up for orientation, but still besufficiently viscous and cohesive to hold together in the processing (aconcept commonly called “melt strength”). These requirements restrictthe molecular weights of the polymer that can be employed.

To overcome the restrictions imposed by the brief period ofsolidification, the polymer can be alternatively treated with a solventmaterial to produce a physical state that is in ways similar to theperiod during solidification. The polymer can be processed during thatperiod to impart properties and/or shapes not achievable from simplemelt processing. Gel-spun polyethylene has been exploited for theproduction of ballistic fibers.

Despite the obvious processing benefits of solvent gellation, very fewexamples have been explored. While the concept can be straightforward,successful implementation can be more difficult. The solvent-polymersystem must achieve a gel that has sufficient solvation of the polymermolecules to manipulate the microstructure while still having sufficientmelt strength to be processed into useful shapes. Once the article hasbeen made, the solvent is typically removed to bring the polymer to itsfull properties. Solvent removal and recovery presents numerous cost andequipment issues to extract and dry the polymer and then recycle orotherwise dispose of the spent solvents. Industrial hygine andenvironmental issues further complicate implementation. It isunderstandable why this technology has been limited to very high valuematerials like ballistic fibers.

For example, there is no recognized solvent system for gel processing ofpolyamide 6 (also known as nylon-6 or poly-caprolactam). Standardsolvents like formic acid yield a solution far too low in viscosity forprocessing. Further, if nylon-6 gel processed products are to compete inapplications other than high-cost ballistic fibers, a suitable solventthat is low-cost to implement is required. One candidate for gelprocessing nylon-6 products that has not been investigated is theepsilon-caprolactam monomer used to make nylon-6.

Caprolactam and nylon compounds have each been individually polymerizedwith the same compounds (i.e. caprolactarn/caprolactam or nylon/nylon)by anionic polymerization in a twin-screw extruder and then tested forresidual monomer content and thermal/mechanical properties. In bothmethods, however, the polymerization process used was not designed toand did not result in a pre-fiber gel composition that could beprocessed by any means (including extrusion), and there was noindication that the mechanical strength or thermal strength was improvedby the single monomer/twin-screw extruder mixing process. (see Antec '93Conference Proceedings, New Orleans, 9^(th)-13^(th) May 1993, Vol. 1, p.470-473; and Antec '94 Conference Proceedings, San Francisco, Calif.,1^(st)-5^(th) May 1994, Vol. 1, p. 116-22)

It was also known that caprolactam formed solutions with nylon-6, butthese solutions took the form of residual, unpolymerized monomer foundin the polymer. Typically nylon-6 resin is leached to remove thisresidual monomer. Deliberate addition of caprolactam for gel processinghas not been previously considered. Gel processing and gel compositionsare important because polymer parts have a practical limit incross-section size due to the difficulty in forming such largecross-sections via melt processing. From a practical perspective,machines (extruders) to form polymer into shapes and sizes routinelyavailable in metal simply do not exist. The other real limitation isthat as melted polymer cools, significant shrinkage occurs. One canoften find puckers on molded parts from shrink. To an extent, shrink canbe compensated with clever mold design and tuning the molding process.

Therefore, it would be desirable to produce a pre-fiber gel materialand/or composition that a) has sufficient viscosity and suitablecohesiveness such that it can be spun into a fiber or yarn, b) can beprocessed by any processing method, including extrusion, and c) can beincorporated into the production of a fiber, a fiber product, a yarnproduct and/or a carpet product. It would also be desirable to producethe pre-fiber gel material and/or composition at temperatures that areat or below normal processing temperatures for a polymer ormonomer-based fiber product.

SUMMARY OF THE SUBJECT MATTER

A pre-fiber gel material is described herein that includes: a) at leastone amide-based and/or polyamide-based composition; and b) at least onelactam gelling agent, wherein the gel composition has sufficientviscosity and sufficient cohesiveness upon the mixing of the at leastone amide-based or polyamide-based polymer and the at least one lactamgelling agent that the composition can be spun into a fiber.

In addition, methods are provided herein that teach that the productionof a pre-fiber gel composition, including: a) providing at least oneamide-based compound; b) providing at least one lactam gelling agent;and c) mixing the at least one amide-based polymer and the at least onelactam gelling agent such that there is sufficient viscosity andsufficient cohesiveness in the composition so that it can be spun into afiber.

DETAILED DESCRIPTION

A pre-fiber gel material and/or composition has been developed that a)has sufficient viscosity and suitable cohesiveness such that it can bespun into a fiber or yarn, b) can be processed by any processing method,including extrusion, and c) can be incorporated into the production of afiber, a fiber product, a yarn product and/or a carpet product.Contemplated pre-fiber gel materials and/or compositions can also beprocessed at temperatures that are at or below normal processingtemperatures for a polymer and/or monomer based fiber product.

The formation of a pre-fiber gel composition and/or material allows forthe control of the properties of the drawn fiber by allowing for morefavorable orientation of the polymer molecules in the fiber. Controllingthe molecule orientation can lead to increased tensile strength andoverall fiber durability. Furthermore, at least part of the at least onegelling agent (such as a lactam gelling agent) can be removed andrecovered from the spun fiber once formed. In addition, anyunpolymerized monomers can be subsequently polymerized after furtherprocessing to create properties in the spun fiber that are difficult orimpossible to achieve with conventional spun polymers. Thispolymerization technique is described in commonly owned US ProvisionalApplication entitled “Pre-Composite and Composite Materials, Methods ofManufacture and Uses Thereof” (Serial No. not yet assigned) that hasbeen filed concurrently and is incorporated herein in its entirety byreference.

In order to produce a pre-fiber gel composition and/or material that canbe formed into a gel spun fiber, a contemplated pre-fiber gelcomposition includes: a) at least one polymer and/or monomer-basedcomposition; and b) at least one gelling agent, wherein the gelcomposition has sufficient viscosity and sufficient cohesiveness uponthe mixing of the at least one polymer and/or monomer-based compositionand the at least one gelling agent that the composition can be spun intoa fiber.

In order to produce a pre-fiber gel composition and/or material that canbe formed into a nylon-based gel spun fiber, a contemplated pre-fibergel composition includes: a) at least one amide-based and/orpolyamide-based composition; and b) at least one lactam gelling agent,wherein the gel composition has sufficient viscosity and sufficientcohesiveness upon the mixing of the at least one amide-based orpolyamide-based polymer and the at least one lactam gelling agent thatthe composition can be spun into a fiber.

At this point it should be understood that, unless otherwise indicated,all numbers expressing quantities of ingredients, constituents,interaction conditions and so forth used in the specification and claimsare to be understood as being modified in all instances by the term“about”. Accordingly, unless indicated to the contrary, the numericalparameters set forth in the specification and attached claims areapproximations that may vary depending upon the desired propertiessought to be obtained by the subject matter presented herein. At thevery least, and not as an attempt to limit the application of thedoctrine of equivalents to the scope of the claims, each numericalparameter should at least be construed in light of the number ofreported significant digits and by applying ordinary roundingtechniques. Notwithstanding that the numerical ranges and parameterssetting forth the broad scope of the subject matter presented herein areapproximations, the numerical values set forth in the specific examplesare reported as precisely as possible. Any numerical value, however,inherently contain certain errors necessarily resulting from thestandard deviation found in their respective testing measurements.

In contemplated embodiments, at least one monomer- and/or polymer-basedcompound is the starting point for the formation of a pre-fiber gelcomposition and/or material. In other embodiments, at least oneamide-based compound and/or polyamide-based compound is the startingpoint for the formation of a pre-fiber gel composition and/or material.As used herein, the term “compound” means a substance with constantcomposition that can be broken down into elements by chemical processes.Polyamides and polyamide-based compounds, as the name implies, arepolymers that comprise amide monomers. Several contemplatedpolyamide-based compounds comprise nylon-based compounds, such asnylon-6.

Amides are an important group of nitrogenous compounds and monomers thatare used as intermediates and/or building blocks in the production ofpolymers, textiles, plastics and adhesives. Amide monomers are generallyrepresented by the following formula:

wherein R is an alkyl group, an aryl group, a cyclic alkyl group, analkenyl group, an arylalkylene group, or any other appropriate groupthat can be utilized to be a part of an amide compound.

As used herein, the term “monomer” generally refers to any chemicalcompound that is capable of forming a covalent bond with itself or achemically different compound in a repetitive manner. The repetitivebond formation between monomers may lead to a linear, branched,super-branched, or three-dimensional product. Furthermore, monomers maythemselves comprise repetitive building blocks, and when polymerized thepolymers formed from such monomers are then termed “blockpolymers”. Theweight-average molecular weight of monomers may vary greatly betweenabout 40 Dalton and 20000 Dalton. However, especially when monomerscomprise repetitive building blocks, monomers may have even highermolecular weights. Monomers may also include additional groups, such asgroups used for crosslinking, radiolabeling, and/or chemical orenvironmental protecting.

The term “alkyl” is used herein to mean a branched or a straight-chainsaturated hydrocarbon group or substituent of 1 to 24 carbon atoms, suchas methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl,octyl, decyl, tetradecyl, hexadecyl, eicosyl, tetracosyl and the like.In some embodiments, contemplated alkyl groups contain 1 to 12 carbonatoms. The term “cyclic alkyl” means an alkyl compound whose structureis characterized by one or more closed rings. The cyclic alkyl may bemono-, bi-, tri- or polycyclic depending on the number of rings presentin the compound. The term “aryl” is used herein to mean a monocyclicaromatic species of 5 to 7 carbon atoms or a compound that is built withmonocyclic aromatic species of 5 to 7 carbon atoms and is typicallyphenyl, naphthalyl, phenanthryl, anthracyl etc. Optionally, these groupsare substituted with one to four, more preferably one to two alkyl,alkoxy, hydroxy, and/or nitro substituents.

The term “alkenyl” is used herein to mean a branched or a straight-chainhydrocarbon chain containing from 2 to 24 carbon atoms and at least onedouble bond. Preferred alkenyl groups herein contain 1 to 12 carbonatoms. The term “alkoxy” is used herein to mean an alkyl group boundthrough a single, terminal ether linkage; that is, an alkoxy group maybe defined as -OR wherein R is an alkyl group, as defined above. Theterm “arylalkylene” is used herein to mean moieties containing bothalkylene and monocyclic aryl species, typically containing less thanabout 12 carbon atoms in the alkylene portion, and wherein the arylsubstituent is bonded to the structure of interest through an alkylenelinking group. Exemplary arylalkylene groups have the structure—(CH₂)j—Ar wherein “j” is an integer in the range of 1 to 6 and wherein“Ar” is an aryl species.

At least one gelling agent is provided that is mixed with the at leastone monomer-based and/or polymer based composition. In some embodiments,the gelling agent comprises a lactam gelling agent that is mixed and/orblended with the at least one polyamide-based or amide-based compound inorder to form a contemplated pre-fiber gel composition. The at least onelactam gelling agent may comprise a caprolactam, such as ε-caprolactam.ε-Caprolactam, also known as aminocaproic lactam and2-oxohexamethyleneimine, is a compound that is produced in flake andmolten forms and is used primarily in the manufacture of nylon-6products such as those products contemplated herein or other syntheticfibers, plastics, bristles, films, coatings, synthetic leathers,plasticizers and paint vehicles. Caprolactam can also be used as across-linking agent for polyurethanes and in the synthesis of the aminoacid lysine. A contemplated lactam preparation method is shown herein inExample 1.

Amides, such as caprolactam, can also be produced by reacting a ketonewith hydroxylamine to make an oxime, and then using an acid catalyzedrearrangement of the oxime(s), conventionally called the Beckmannrearrangement, to form the amide. Merchant quality caprolactam can beproduced by methods described in U.S. patent application Ser. No.:10/251,335 filed on Sep. 21, 2002, which is commonly owned and hereinincorporated in its entirety.

The at least one gelling agent and/or lactam gelling agent may be addedin any suitable weight percentage with respect to the other compositionconstituents, as long as the addition of the gelling agent aids in theproduction of a pre-fiber gel composition. In a contemplated embodiment,the at least one gelling agent comprises less than 50 weight percent ofthe composition. In another contemplated embodiment, the at least onegelling agent comprises less than 40 weight percent of the composition.In yet another contemplated embodiment, the at least one gelling agentcomprises less than 30 weight percent of the composition. In othercontemplated embodiments, the at least one gelling agent comprises lessthan 20 weight percent of the composition. In yet other contemplatedembodiments, the at least one gelling agent comprises less than 10weight percent of the composition. Also, in some contemplatedembodiments, the at least one gelling agent comprises less than 5 weightpercent of the composition.

Issues to review as to whether caprolactam/nylon-6 gels would be usefulis that they need a suitable viscosity and melt strength for processing.Unexpectedly suitable gels can be prepared over a wide range ofconcentrations from below 5 wt. % caprolactam to at least 50 wt. %.These gels proved remarkably easy to spin into fibers on conventionalmelt-spinning equipment and at drawing/take-up speeds comparable tocommercial melt spinning. Gel polymers can be processed at lowertemperatures than simple, neat melts. This feature can be exploited toprocess higher molecular weight nylon-6 without undue increases inoperating temperatures.

More significantly, the melt strength was unexpectedly good (exhibitedby the ability to spin gel at high speed) over the wide range of bothcaprolactam concentration and processing temperature (from significantlybelow the normal melt processing temperature to well above it). In manyways, the nylon gel has superior processibility over plain melted nylon.This is in contrast to gel spun polyethylene were the gel must be spunat low linear speed prior to removal of the solvent.

The unexpectedly good processibility of nylon/caprolactam gels providesgreater flexibility in manufacturing products. The ability to spin thegel at high speeds suggest that nylon gel products can be manufacturedwith productivity comparable to melt processing. The excellent meltstrength of the gels also allow the polymer to be highly shaped or drawnprior to solvent removal; or, only lightly processed, the caprolactamremoved, and then post-processed to achieved the desired combination ofproperties. The caprolactam itself has advantages as a gelling solvent.It is relatively inexpensive, low volatility, and non-hazardous withfavorable industrial hygiene properties. The caprolactam can beextracted from the polymer with water and then easily recovered forre-use.

In addition, methods are provided herein that teach that the productionof a pre-fiber gel composition, comprising: a) providing at least onemonomer- and/or polymer-based compound; b) providing at least onegelling agent; and c) mixing the at least one monomer- and/orpolymer-based compound and the at least one gelling agent such thatthere is sufficient viscosity and sufficient cohesiveness in thecomposition so that it can be spun into a fiber. In some embodiments,mixing comprises any suitable method, including blending or extruding.In yet other embodiments, the at least part of the at least one gellingagent may be removed after the mixing step.

In addition, methods are provided herein that teach that the productionof a pre-fiber gel composition, comprising: a) providing at least oneamide-based compound; b) providing at least one lactam gelling agent;and c) mixing the at least one amide-based polymer and the at least onelactam gelling agent such that there is sufficient viscosity andsufficient cohesiveness in the composition so that it can be spun into afiber. In some embodiments, mixing comprises any suitable method,including blending or extruding. In yet other embodiments, the at leastpart of the at least one lactam gelling agent may be removed after themixing step.

The at least one polymer and/or monomer based compound, the at least oneamide-based compound, the at least one gelling agent and/or at least onelactam gelling agent may be provided by any suitable method, includinga) buying at least some of the at least one polymer and/or monomer basedcompound, the at least one amide-based compound, the at least onegelling agent and/or at least one lactam gelling agent from a supplieror textile mill; b) preparing or producing at least some of the at leastone polymer and/or monomer based compound, the at least one amide-basedcompound, the at least one gelling agent and/or at least one lactamgelling agent in house using chemicals provided by another source and/orc) preparing or producing at least some of the at least one polymerand/or monomer based compound, the at least one amide-based compound,the at least one gelling agent and/or at least one lactam gelling agentin house using chemicals also produced or provided in house or at thelocation.

During or after the formation of contemplated pre-fiber gelcompositions, fiber materials, yarn products and/or carpet products, athermal energy may be applied to the materials and/or products, whereinthe thermal energy comprises a temperature that is at or above themelting point of the constituents, the fiber and/or other heat-activecomponents. The thermal energy can be applied to activate at least someof the plurality of fibers. In some embodiments, activating the fiberscomprises forming chemical, such as covalent, ionic or hydrogen and/orphysical, such as adhesion, bonds between at least some of the pluralityof fibers and at least one of the other components.

The thermal energy may come from any suitable source, includingextended/non-point sources, such as a UV-VIS source, an infra-redsource, a heat source, both radiative and convective, or a microwavesource; or electron sources, such as electron guns or plasma sources.Other suitable energy sources include electron beams, and radiativedevices at non-IR wavelengths including x-ray, and gamma ray. Stillother suitable energy sources include vibrational sources such asmicrowave transmitters. In preferred embodiments, the energy source isan extended source. In more preferred embodiments, the energy source isa heat source, such as an atmospheric pressure forced air machine, whichcan be followed by a steam purge, or a pressurized twist-settingmachine. An example of an atmospheric pressure forced air machine is theSuessen® Twist-Setting Machine. Examples of pressurized twist-settingmachines are those of the autoclave-type and those manufactured bySuperba®.

It should be understood that the thermal energy may be appliedconsistently or in short bursts. It is also contemplated that thethermal energy may be gradually and continuously applied over atemperature range until the thermal energy is at or above the meltingpoint of the fiber or other heat-active components. For example, thefiber material and/or yarn may be heated by an atmospheric pressureforced air machine at a temperature of about 195° C. for a residencetime of about 60 seconds, before the treated fiber material and/or yarnproduct is tufted. The thermal energy may also be immediately applied ator above the melting point of the binder fiber and/or other heat-activecomponents without any ramp time.

The pre-fiber gel materials contemplated and described herein may beused alone or in combination with other materials and/or products toform any suitable product, including a spun fiber product, a yarnproduct, a fabric product and/or a carpet product.

EXAMPLES

The pre-fiber gel compositions, fiber materials, yarn products, carpetproducts and methods used to produce those materials and products, asdescribed in the examples, are for illustrative purpose only and shouldnot, in any way, limit the scope of this invention.

Example 1 Lactam Preparation

Four liters of caprolactam were melted in a convection oven overnight ina covered container. The lactam was poured into a 5L 3-neckeddistillation flask with a magnetic stir bar and an electric heatingmantle (top and bottom mantles). The distillation column was vacuumjacketed by a 29/42 column and a 10 tray section, a 5 tray section, asplitting distillation head and a condenser. The condenser was held at50° C. with a heated water circulator. The system had the pressurereduced from 7 mm Hg to 4 mm Hg. Heat was applied and the column wasbrought to reflux conditions and held for 30 minutes. After 30 minutesfor the column to stabilize, the distillation head splitter wasactivated with a 4 second take off and a 10 second reflux. Slightly lessthan 1 liter of lactam was distilled off. The heat was turned off andthe mantles were removed allowing the lactam in the 5-liter flask todrop to 90° C. before breaking the vacuum on the system. The 5-literflask was removed and the lactam was poured into 1-liter nalgene beakersand promptly placed into a glove box with a dry nitrogen atmosphere.After cooling overnight, the crystal lactam was transferred to plasticbags and was broken into flake form with a hammer inside the glove box.The lactam was stored inside the dry glove box under house nitrogenuntil needed for the pre-fiber gel composition formation.

Example 2 Pre-fiber Gel Composition Formation

Nylon-6 was ground to a fine powder and mixed with a lactam gellingagent, which was in this case—caprolactam. A Braybender mixer was usedto mix the nylon and caprolactam at a speed of 60 RPM. Addition timetook about 5 minutes and the gel was allowed to mix for 15 minutes aftercharging at the temperature indicated. The samples were removed whilethe Braybender was running with a brass wipe stick. The samples werethen ground in a Willey mill using a course screen. A weighted amount ofeach ground gel mix was extracted 16 +hours using a jacketed soxletextractor. The extract was filtered using a folded #54 paper and rinsedinto a 100 mL volumetric flask. The extract was brought to volume withdeionized water and then analyzed by Gas Chromatography for % lactamusing a Carbowax column.

% LACTAM BRAYBENDER WEIGHT % LACTAM IN GEL BY GEL MIX TEMPERATUREEXTRACTED VOLUME IN EXTRACT GC  5% Lactam 225 8.9041 100 0.2867 3.22 10%Lactam 220 9.0031 100 0.4204 4.67 15% Lactam 215 9.7892 100 0.9114 9.3120% Lactam 210 8.6867 100 0.966 11.12 30% Lactam 205 8.7811 100 1.812420.64 40% Lactam 194 7.6208 100 2.3396 30.7

The resulting gels were gel spun on an RX-2 (what is this machine?). Thegels spun into a fiber product surprisingly well and packages of fiberwere able to be prepared at most conventional spinning conditions.Furthermore, it was observed that extruder temperature could be droppedbelow conventional conditions for neat polymers, given that the gelcompositions allowed for lower extruder pressures. Tables 1-5, shownbelow, give summaries of several of the spinning conditions utilized inthese Examples.

Thus, specific embodiments and applications of pre-fiber gelcompositions and materials, their manufacture and uses thereof have beendisclosed. It should be apparent, however, to those skilled in the artthat many more modifications besides those already described arepossible without departing from the inventive concepts herein. Theinventive subject matter, therefore, is not to be restricted except inthe spirit of the appended claims. Moreover, in interpreting both thespecification and the claims, all terms should be interpreted in thebroadest possible manner consistent with the context. In particular, theterms “comprises” and “comprising” should be interpreted as referring toelements, components, or steps in a non-exclusive manner, indicatingthat the referenced elements, components, or steps may be present, orutilized, or combined with other elements, components, or steps that arenot expressly referenced.

TABLE 1 Nylon Gel Spinning: RXT-2 UNIT CHANGE NUMBERS WHERE IT IS BLUECOLOR MINIMUM PUMP RPM 8 MAXIMUM PUMP RPM 40 PUMP SIZE(CC/REV.) 1.16NUMBER OF FILAMENTS 14 PUMP SPEED(RPM) 19.7 POLYMER DENSITY(GM/CC) 0.98THRU-PUT(LBS/HR) 2.95969 THRU-PUT PER FIL(LBS/HR) 0.21141 THRU-PUT PERFIL(GMS/MIN) 1.5982 THRU-PUT(GMS/MIN) 22.395 THRU-PUT(GMS/MIN) 22.395THRU-PUT PER FIL(GMS/MIN) 1.59964 TAKE-UP SPEED (Meter/min) 3000 FROMFT/MIN TO M/MIN 0.3048 DPF GMS @TAKE-UP ROLL (UNDRAWN) 4.79892 DTEX PERFIL GMS @TAKE-UP ROLL (UNDRAWN) 5.33213 FIL DIAMETER, MICRONS (UNDRAWN)22.1859 22.186 FIL DIAMETER, mm (UNDRAWN) 0.02219 TAKE-UP SPEED(FEET/min) 9842.52 Spinnerette diameter length L/D AREA INCH 0.03 0.09 30.0007065 CM 0.0762 0.2286 3 0.00455806 YARN DENIER @TAKE-UP ROLL (GMS)67.1849 FLOW RATE(CC/MIN) 22.852 JET VELOCITY (CM/MIN) 5013.54 JETVELOCITY (meter/MIN) 50.1354 DR @ (TAKE-UP ROLL) 59.8379407 SPIN.CAPILLARY RADIUS (FT) 0.0025 SPIN. CAPILLARY LENGTH (FT) 0.0075 THRU-PUTPER FIL(LBm/HR) 0.21141 DENSITY(LBm/FT3) 61.1814 FLOW RATE(FT3/SEC.)9.6E−07 VISCOSITY (POISE) 3143.9 VISCOSITY (LBf.SEC/FT2) 6.56634 DELTAPRESSURE(PSI) 21.4101 Stack Draw (calc. From sprt hole dia. And fildia.) 34.3462 FINAL REQUIRE DENIER AFTER DRAWIN 10 DRAWING DRAW RATIO0.47989

TABLE 2 Starting Sample I.D. Conditions #1 #2 #3 #4 POLYMER TYPE MBM MBMMBM 10% MBM 10% Lactam Lactam Feeder Setting 2.96 2.96 2.96 2.96 2.96Date Oct. 23, 2002 Oct. 23, 2002 Oct. 23, 2002 Oct. 23, 2002 Oct. 23,2002 water on feeding zone on on on on on zone 1 Temp. (deg c.) 245 270250 250 245 zone 2 Temp. (deg c.) 245 280 250 250 245 zone 3 Temp. (degc.) 245 280 250 250 245 zone 4 Temp. (deg c.) 245 280 250 250 245 zone 5Temp. (deg c.) 245 280 250 250 245 zone 6 Temp. (deg c.) 245 280 250 250245 zone 7 Temp. (deg c.) 245 280 250 250 245  8 Connecting Plate Temp.(deg. C.) 245 280 250 250 245  9 Block Temp. (deg. C.) 245 280 250 250245 10 Spin Pump Temp. (deg. C.) 245 280 250 250 245 11 Top Cap (deg.C.) 245 280 250 250 245 12 Spin Pack Temp. (deg. C.) 245 280 250 250 245Top Heated Sleeve Length (inches) xxxx xxxx xxxx xxxx xxxx Top HeatedSleeve Temp. (deg. c.) xxxx xxxx xxxx xxxx xxxx Bottom Heated SleeveLength (inches) xxxx xxxx xxxx xxxx xxxx Bottom Heated Sleeve Temp.(deg. c.) xxxx xxxx xxxx xxxx xxxx Barrel Melt Temp. (deg. c.) 252 288256 257 251 Melt Pump Inlet Pressure (psi) ???? 420 10 200 10 Melt PumpOutlet Pressure (psi) ???? 200 470 250 250 Extruder (rpm) 200 200 200200 200 Spinneret: no. of holes/Shape 14 R 14 R 14 R 14 R 14 RSpinneret: capilary diameter & depth .024 × 0.072 .024 × 0.072 .024 ×0.072 .024 × 0.072 .024 × 0.072 Metering pump size (cc/rev) 1.16 1.161.16 1.16 1.16 Metering pump (rpm) 16.7 19.3 19.8 19.8 19.8 Thruput(lbs/hr) 2.97 2.97 2.97 2.97 2.97 Filter type STD SCREEN STD SCREEN STDSCREEN STD SCREEN STD SCREEN Monomer Exhaust Reading (inches water) TBDTBD TBD TBD TBD Quench air Flow rate (CF/M) 14.2 14.2 14.2 14.2 14.2Qench air Temp. (deg. c.) 19 19 19 19 19 Quench air Humidity % 40.8 40.840.8 40.8 40.8 % Torque 70 25 29 22 20 Nitrogen in Hoper 3 3 3 3 3 Need:polymer chips moisture Yes Need: Free fall samples for FAV, COOH Yes YesYes Yes Yes Sample I.D. #5 #6 #7 #8 POLYMER TYPE MBM 10% MBM 10% MBM 10%MBM 10% Lactam Lactam Lactam Lactam Feeder Setting 2.96 2.96 2.96 2.96Date Oct. 23, 2002 Oct. 23, 2002 Oct. 23, 2002 Oct. 23, 2002 water onfeeding zone on on on on zone 1 Temp. (deg c.) 240 235 230 225 zone 2Temp. (deg c.) 240 235 230 225 zone 3 Temp. (deg c.) 240 235 230 225zone 4 Temp. (deg c.) 240 235 230 225 zone 5 Temp. (deg c.) 240 235 230225 zone 6 Temp. (deg c.) 240 235 230 225 zone 7 Temp. (deg c.) 240 235230 225  8 Connecting Plate Temp. (deg. C.) 240 235 230 225  9 BlockTemp. (deg. C.) 240 235 230 225 10 Spin Pump Temp. (deg. C.) 240 235 230225 11 Top Cap (deg. C.) 240 235 230 225 12 Spin Pack Temp. (deg. C.)240 235 230 225 Top Heated Sleeve Length (inches) xxxx xxxx xxxx xxxxTop Heated Sleeve Temp. (deg. c.) xxxx xxxx xxxx xxxx Bottom HeatedSleeve Length (inches) xxxx xxxx xxxx xxxx Bottom Heated Sleeve Temp.(deg. c.) xxxx xxxx xxxx xxxx Barrel Melt Temp. (deg. c.) 246 240 235231 Melt Pump Inlet Pressure (psi) 10 10 10 10 Melt Pump Outlet Pressure(psi) 310 260 360 400 Extruder (rpm) 200 200 200 200 Spinneret: no. ofholes/Shape 14 R 14 R 14 R 14 R Spinneret: capilary diameter & depth.024 × 0.072 .024 × 0.072 .024 × 0.072 .024 × 0.072 Metering pump size(cc/rev) 1.16 1.16 1.16 1.16 Metering pump (rpm) 19.8 19.7 19.7 19.7Thruput (lbs/hr) 2.97 2.97 2.97 2.97 Filter type STD SCREEN STD SCREENSTD SCREEN STD SCREEN Monomer Exhaust Reading (inches water) TBD Quenchair Flow rate (CF/M) 14.2 15.5 15.9 14.9 Qench air Temp. (deg. c.) 1919.3 19.6 19.7 Quench air Humidity % 40.8 39.8 39.5 39 % Torque 21 20 2424 Nitrogen in Hoper 3 3 3 3 Need: polymer chips moisture yes Need: Freefall samples for FAV, COOH Yes Yes

TABLE 3 Sample I.D. #9 #10 #11 #12 #13 POLYMER TYPE BHS BHS 10% BHS 10%BHS 10% BHS 10% Lactam Lactam Lactam Lactam Feeder Setting 2.96 2.962.96 2.96 2.96 water on feeding zone on on on on on zone 1 Temp. (degc.) 252 252 247 242 237 zone 2 Temp. (deg c.) 252 252 247 242 237 zone 3Temp. (deg c.) 252 252 247 242 237 zone 4 Temp. (deg c.) 252 252 247 242237 zone 5 Temp. (deg c.) 252 252 247 242 237 zone 6 Temp. (deg c.) 252252 247 242 237 zone 7 Temp. (deg c.) 252 252 247 242 237  8 ConnectingPlate Temp. (deg. C.) 252 252 247 242 237  9 Block Temp. (deg. C.) 252252 247 242 237 10 Spin Pump Temp. (deg. C.) 252 252 247 242 237 11 TopCap (deg. C.) 252 252 247 242 237 12 Spin Pack Temp. (deg. C.) 252 252247 242 237 Top Heated Sleeve Length (inches) xxxx xxxx xxxx xxxx xxxxTop Heated Sleeve Temp. (deg. c.) xxxx xxxx xxxx xxxx xxxx Bottom HeatedSleeve Length (inches) xxxx xxxx xxxx xxxx xxxx Bottom Heated SleeveTemp.(deg. c.) xxxx xxxx xxxx xxxx xxxx Barrel Melt Temp. (deg. c.) 259260 254 249 245 Melt Pump Inlet Pressure (psi) 40 90 250 280 180 MeltPump Outlet Pressure (psi) 970 520 570 610 740 Extruder (rpm) 200 200200 200 200 Spinneret: no. of holes/Shape 14 R 14 R 14 R 14 R 14 RSpinneret: capilary diameter & depth .024 × 0.072 .024 × 0.072 .024 ×0.072 .024 × 0.072 .024 × 0.072 Metering pump size (cc/rev) 1.16 1.161.16 1.16 1.16 Metering pump (rpm) 19.7 19.7 19.7 19.7 19.7Thruput(lbs/hr) 2.97 2.97 2.97 2.97 2.97 Filter type STD SCREEN STDSCREEN STD SCREEN STD SCREEN STD SCREEN Monomer Exhaust Reading (incheswater) TBD TBD TBD TBD TBD Quench air Flow rate(CF/M) 14.6 14.5 14.614.9 15 Qench air Temp. (deg. c.) 19.5 16.9 19.2 19.2 18.7 Quench airHumidity % 38.7 39.3 39.7 41.6 39.7 % Torque 42 27 29 30 29 Nitrogen inHoper 3 3 3 3 3 Need: polymer chips moisture Need: Free fall samples forFAV, COOH Sample I.D. #14 #15 #16 #17 POLYMER TYPE BHS 10% BHS 10% 135135 10% Lactam Lactam Lactam Feeder Setting 2.96 2.96 2.96 2.96 water onfeeding zone on on on on zone 1 Temp. (deg c.) 232 227 260 260 zone 2Temp. (deg c.) 232 227 260 260 zone 3 Temp. (deg c.) 232 227 260 260zone 4 Temp. (deg c.) 232 227 260 260 zone 5 Temp. (deg c.) 232 227 260260 zone 6 Temp. (deg c.) 232 227 260 260 zone 7 Temp. (deg c.) 232 227260 260  8 Connecting Plate Temp. (deg. C.) 232 227 260 260  9 BlockTemp. (deg. C.) 232 227 260 260 10 Spin Pump Temp. (deg. C.) 232 227 260260 11 Top Cap (deg. C.) 232 227 260 260 12 Spin Pack Temp. (deg. C.)232 227 260 260 Top Heated Sleeve Length (inches) xxxx xxxx xxxx xxxxTop Heated Sleeve Temp. (deg. c.) xxxx xxxx xxxx xxxx Bottom HeatedSleeve Length (inches) xxxx xxxx xxxx xxxx Bottom Heated SleeveTemp.(deg. c.) xxxx xxxx xxxx xxxx Barrel Melt Temp. (deg. c.) 240 235270 269 Melt Pump Inlet Pressure (psi) 50 70 1200 300 Melt Pump OutletPressure (psi) 790 840 1600 1040 Extruder (rpm) 200 200 200 200Spinneret: no. of holes/Shape 14 R 14 R 14 R 14 R Spinneret: capilarydiameter & depth .024 × 0.072 .024 × 0.072 .024 × 0.072 .024 × 0.072Metering pump size (cc/rev) 1.16 1.16 1.16 1.16 Metering pump (rpm) 19.719.7 19.7 19.7 Thruput(lbs/hr) 2.97 2.97 2.97 2.97 Filter type STDSCREEN STD SCREEN STD SCREEN STD SCREEN Monomer Exhaust Reading (incheswater) TBD TBD TBD TBD Quench air Flow rate(CF/M) 14.6 14.9 14.5 15.1Qench air Temp. (deg. c.) 19 19.4 18.5 19.2 Quench air Humidity % 40.339.4 39.6 41.1 % Torque 30 29 56 37 Nitrogen in Hoper 3 3 3 3 Need:polymer chips moisture Need: Free fall samples for FAV, COOH

TABLE 4 Sample I.D. #18 #19 #20 #21 #22 POLYMER TYPE 135 10% 135 10% 13510% 135 10% 135 10% Lactam Lactam Lactam Lactam Lactam Feeder Setting2.96 2.96 2.95 2.96 2.96 Date Oct. 24, 2002 Oct. 24, 2002 Oct. 24, 2002Oct. 24, 2002 Oct. 24, 2002 water on feeding zone on on on on on zone 1Temp. (deg c.) 255 250 245 240 235 zone 2 Temp. (deg c.) 255 250 245 240235 zone 3 Temp. (deg c.) 255 250 245 240 235 zone 4 Temp. (deg c.) 255250 245 240 235 zone 5 Temp. (deg c.) 255 250 245 240 235 zone 6 Temp.(deg c.) 255 250 245 240 235 zone 7 Temp. (deg c.) 255 250 245 240 235 8 Connecting Plate Temp. (deg. C.) 255 250 245 240 235  9 Block Temp.(deg. C.) 255 250 245 240 235 10 Spin Pump Temp. (deg. C.) 255 250 245240 235 11 Top Cap (deg. C.) 255 250 245 240 235 12 Spin Pack Temp.(deg. C.) 255 250 245 240 235 Top Heated Sleeve Length (inches) xxxxxxxx xxxx xxxx xxxx Top Heated Sleeve Temp. (deg. c.) xxxx xxxx xxxxxxxx xxxx Bottom Heated Sleeve Length (inches) xxxx xxxx xxxx xxxx xxxxBottom Heated Sleeve Temp. (deg. c.) xxxx xxxx xxxx xxxx xxxx BarrelMelt Temp. (deg. c.) 264 259 253 248 243 Melt Pump Inlet Pressure (psi)630 470 450 630 600 Melt Pump Outlet Pressure (psi) 1080 1140 1260 12801330 Extruder (rpm) 200 200 200 200 200 Spinneret: no. of holes/Shape 14R 14 R 14 R 14 R 14 R Spinneret: capilary diameter & depth .024 × 0.072.024 × 0.072 .024 × 0.072 .024 × 0.072 .024 × 0.072 Metering pump size(cc/rev) 1.16 1.16 1.16 1.16 1.16 Metering pump (rpm) 19.7 19.7 19.719.7 19.7 Thruput (lbs/hr) 2.97 2.97 2.97 2.97 2.97 Filter type STDSCREEN STD SCREEN STD SCREEN STD SCREEN STD SCREEN Monomer ExhaustReading (inches water) TBD TBD TBD TBD TBD Quench air Flow rate (CF/M)15.2 14.9 14.5 14.4 14.9 Qench air Temp. (deg. c.) 20.1 19.5 18.7 1918.9 Quench air Humidity % 39.4 40.7 39.7 40.1 41.3 % Torque 39 38 40 3739 Nitrogen in Hoper 3 3 3 3 3 Need: polymer chips moisture Need: Freefall samples for FAV, COOH Sample I.D. #23 #24 #25 #26 POLYMER TYPE 13510% 135 10% 195 195 10% Lactam Lactam Lactam Feeder Setting 2.96 2.962.96 2.96 Date Oct. 24, 2002 Oct. 24, 2002 Oct. 24, 2002 Oct. 24, 2002water on feeding zone on on on on zone 1 Temp. (deg c.) 230 225 300/289290/273 zone 2 Temp. (deg c.) 230 225 300 290 zone 3 Temp. (deg c.) 230225 300 290 zone 4 Temp. (deg c.) 230 225 300 290 zone 5 Temp. (deg c.)230 225 300 290 zone 6 Temp. (deg c.) 230 225 300 290 zone 7 Temp. (degc.) 230 225 300 290  8 Connecting Plate Temp. (deg. C.) 230 225 300 290 9 Block Temp. (deg. C.) 230 225 300 290 10 Spin Pump Temp. (deg. C.)230 225 300 290 11 Top Cap (deg. C.) 230 225 300 290 12 Spin Pack Temp.(deg. C.) 230 225 300/300 290 Top Heated Sleeve Length (inches) xxxxxxxx xxxx xxxx Top Heated Sleeve Temp. (deg. c.) xxxx xxxx xxxx xxxxBottom Heated Sleeve Length (inches) xxxx xxxx xxxx xxxx Bottom HeatedSleeve Temp. (deg. c.) xxxx xxxx xxxx xxxx Barrel Melt Temp. (deg. c.)238 232 312 299 Melt Pump Inlet Pressure (psi) 580 190 1480 1080 MeltPump Outlet Pressure (psi) 1480 1700 1290 790 Extruder (rpm) 200 200 200200 Spinneret: no. of holes/Shape 14 R 14 R 14 R 14 R Spinneret:capilary diameter & depth .024 × 0.072 .024 × 0.072 .024 × 0.072 .024 ×0.072 Metering pump size (cc/rev) 1.16 1.16 1.16 1.16 Metering pump(rpm) 19.7 19.7 19.7 19.7 Thruput (lbs/hr) 2.97 2.97 2.97 2.97 Filtertype STD SCREEN STD SCREEN STD SCREEN STD SCREEN Monomer Exhaust Reading(inches water) TBD TBD TBD TBD Quench air Flow rate (CF/M) 14 14.2 14.614.8 Qench air Temp. (deg. c.) 19.1 18.7 18.9 19.5 Quench air Humidity %38.7 39.1 96.8 39.1 % Torque 40 42 52 38 Nitrogen in Hoper 3 3 3 3 Need:polymer chips moisture Need: Free fall samples for FAV, COOH

TABLE 5 Sample I.D. #27 #28 #29 #30 POLYMER TYPE 195 10% 195 10% 195 10%195 10% Lactam Lactam Lactam Lactam Feeder Setting 2.96 2.96 2.96 2.96Date Oct. 24, 2002 Oct. 24, 2002 Oct. 24, 2002 Oct. 24, 2002 water onfeeding zone on on on on zone 1 Temp. (deg c.) 285/270 280/266 275/263270/258 zone 2 Temp. (deg c.) 285 280 275 270 zone 3 Temp. (deg c.) 285280 275 270 zone 4 Temp. (deg c.) 285 280 275 270 zone 5 Temp. (deg c.)285 280 275 270 zone 6 Temp. (deg c.) 285 280 275 270 zone 7 Temp. (degc.) 285 280 275 270  8 Connecting Plate Temp. (deg. C.) 285 280 275 270 9 Block Temp. (deg. C.) 285 280 275 270 10 Spin Pump Temp. (deg. C.)285 280 275 270 11 Top Cap (deg. C.) 285 280 275 270 12 Spin Pack Temp.(deg. C.) 285 280 275 270 Top Heated Sleeve Length (inches) xxxx xxxxxxxx xxxx Top Heated Sleeve Temp. (deg. c.) xxxx xxxx xxxx xxxx BottomHeated Sleeve Length (inches) xxxx xxxx xxxx xxxx Bottom Heated SleeveTemp. (deg. c.) xxxx xxxx xxxx xxxx Barrel Melt Temp. (deg. c.) 296 289284 279 Melt Pump Inlet Pressure (psi) 1250 50 860 1060 Melt Pump OutletPressure (psi) 860 890 970 1100 Extruder (rpm) 200 200 200 200Spinneret: no. of holes/Shape 14 R 14 R 14 R 14 R Spinneret: capilarydiameter & depth .024 × 0.072 .024 × 0.072 .024 × 0.072 .024 × 0.072Metering pump size (cc/rev) 1.16 1.16 1.16 1.16 Metering pump (rpm) 19.719.7 19.7 19.7 Thruput (lbs/hr) 2.97 2.97 2.97 2.97 Filter type STDSCREEN STD SCREEN STD SCREEN STD SCREEN Monomer Exhaust Reading (incheswater) open open open open Quench air Flow rate (CF/M) 14.7 14.7 14.213.9 Qench air Temp. (deg. c.) 19.2 19.7 20 18.7 Quench air Humidity %46.1 41.5 43.1 39.4 % Torque 41 28 37 41 Nitrogen In Hoper 3 3 3 3 Need:polymer chips moisture Need: Free fall samples for FAV, COOH

1. A method of producing a pre-fiber gel composition, consistingessentially of: providing at least one amide-based compound; providingat least one lactam gelling agent; and mixing the at least oneamide-based polymer and the at least one lactam gelling agent such thatthere is sufficient viscosity and sufficient cohesiveness in thecomposition so that it can be spun into a fiber.
 2. The method of claim1, wherein the at least one amide-based polymer comprises a nyloncompound.
 3. The method of claim 2, wherein the nylon compound comprisesnylon-6.
 4. The method of claim 1, wherein the at least one lactamgelling agent comprises caprolactam.
 5. The method of claim 1, whereinthe at least one lactam gelling agent comprises less than 50 weightpercent of the composition.
 6. The method of claim 5, wherein the atleast one lactam gelling agent comprises less than 40 weight percent ofthe composition.
 7. The method of claim 6, wherein the at least onelactam gelling agent comprises less than 30 weight percent of thecomposition.
 8. The method of claim 6, wherein the at least one lactamgelling agent comprises less than 20 weight percent of the composition.9. The method of claim 1, wherein mixing comprises blending.
 10. Themethod of claim 1, wherein mixing comprises extruding.
 11. A spun fiberformed using the method of claim
 1. 12. A carpet product comprising thespun fiber of claim
 9. 13. A pre-fiber gel composition, consistingessentially of: at least one amide-based polymer; and at least onelactam gelling agent, wherein the gel composition has sufficientviscosity and sufficient cohesiveness upon the mixing of the at leastone amide- based polymer and the at least one lactam gelling agent thatthe composition can be spun into a fiber.
 14. A method of producing apre-fiber gel composition, consisting essentially of: providing at leastone amide-based compound; providing at least one lactam gelling agent;mixing the at least one amide-based polymer and the at least one lactamgelling agent such that there is sufficient viscosity and sufficientcohesiveness in the composition so that it can be spun into a fiber;heating the composition; and removing at least part of the at least onelactam gelling agent after the mixing step.